[Wien] Fwd: not getting convergence with MBJ potential

Peter Blaha pblaha at theochem.tuwien.ac.at
Mon Dec 12 16:02:45 CET 2011


If your geometry is not correct, you cannot expect that the bandgaps are correct or
even metal/insulator state comes out correctly.

The experimental lattice parameters are usually ok, even in the simplest experiments, but the positions of
light elements (oxygen) vs. heavier ones are NOT. Thus I would take the exp. lattice parameters, but when
forces are big (<10-20 mRy/bohr), you need to run a couple of min steps.

In all charge-transfer insulators you have the gap between O-2p and TM-d states and you CAN influence the
gap by LDA+U. Larger U simply shifts the upper Hubbard band up and makes a larger gap to O-2p. (PS: I'm
not arguing that LDA+U necessarily describes the physics correctly, but usually it does what one tells it).

PPS: Have you done optics ? Eventually matrix elements may influence the absorption and you cannot just look into the DOS.

> b) We have done UV-visible band gap measurement on this material and it is 3.26 eV. But as you have said properly it is indeed coming as metal after getting converged in 80
> iterations. But we have noticed that there are presence of O p orbital between upper and lower Hubbard band of transition metal atom and hence GGA+U will not improve the situation.
>
> c) At the moment we are a bit handicapped for doing Geometrical (both lattice parameter and atomic coordinates) optimization of 56 atoms unit cell structure as we do not have the
> facility of cluster. Hence as a first approximation we are first trying to reach as near as possible to the accurate electronic structure. We are soon going to get the facility
> and then we can use geometrical optimization.
> And hence we really do have large forces on the structure.
>
> d) We have used a greed of 0.2 and 0.15 both for PRATT mixing and we have not used MSR1 mixing for mbj potential yet.
>
> Sir, as far as the above discussion is concerned we might have our structure wrong (need more accurate TEM analysis!) or Geometrical optimization may solve the problem. But as we
> are now trying to experiment with test run we and as it seems GGA+U can not solve the problem we have opted for mbj potential.
>
> But as you have said if the structure is wrong (we are not yet confirmed though) we may never reach the convergence or desired electronic structure!
>
> Thank you very much for your help Sir.
>
> On Mon, Dec 12, 2011 at 6:52 PM, Laurence Marks <L-marks at northwestern.edu <mailto:L-marks at northwestern.edu>> wrote:
>
>     I wonder whether you really have the structure right.
>
>     a) When you say that you get the same structure, what R-factor? Powder
>     diffraction is not very sensitive to oxygen positions in the presence
>     of heavy metal atoms.
>
>     b) If GGA takes about 80 iterations I suspect that you have a metal.
>     If you do not have the correct number of oxygen versus metal atoms you
>     will get this, and no amount of U or mBJ will change this (in 99% of
>     cases). Check the bond-valence sums of your model, are the numbers
>     reasonable? This is a standard test in solid-state chemistry.
>
>     c) Do you have large forces (as Peter asked)? If you do this also
>     indicates that you have the structure wrong.
>
>     d) When you say that you were using a greed of 0.2 (please do not use
>     the term "mixing factor", it is misleading) was this for Pratt or
>     MSR1? A change from 0.2 to 0.15 with MSR1 will not matter much.
>
>     2011/12/12 shamik chakrabarti <shamikphy at gmail.com <mailto:shamikphy at gmail.com>>:
>      > Dear Dr Peter Blaha and Dr Pascal,
>      >
>      >                               The material is a ferrimagnetic transition
>      > metal compound and a charge transfer insulator and the gap is between d and
>      > O p states. Yes we have started MBJ potential calculation from the converged
>      > GGA charge density. So what we can do, we can start from the scratch with
>      > MBJ potential and after few iterations will get shifted to MSR1 mixing to
>      > improve the convergence. We hope that will help. Thank you for all your
>      > helps.
>      >
>      > with regards,
>      >
>      >
>      > On Mon, Dec 12, 2011 at 1:31 PM, pascal boulet
>      > <pascal.boulet at univ-provence.fr <mailto:pascal.boulet at univ-provence.fr>> wrote:
>      >>
>      >>
>      >> Dear Dr. Chakrabarti,
>      >>
>      >> All right. So, another idea: could it be that you restarted your m-BJ
>      >> calculation using the converged GGA or GGA+U density? I ran into these
>      >> kinds of troubles several times. I found it preferable to start from
>      >> scratch...
>      >>
>      >> Hope this help,
>      >> Pascal
>      >>
>      >> On 12/12/2011 08:45, shamik chakrabarti wrote:
>      >> > Dear Dr. Pascal,
>      >> >
>      >> >                 As we were getting Ghost band error due to large
>      >> > charge fluctuation during initial cycle *we have reduced the mixing
>      >> > parameter from 0.2 to 0.15 & hence thereafter we have not received
>      >> > ghost band error yet.*
>      >> >
>      >> > As long as variation of RMT is concerned the variation is only from
>      >> > 1.7 to 2.01 in the structure.
>      >> >
>      >> > So far there is no energy equivalence between a local orbital and
>      >> > overall energy parameter which can induce ghost band error.
>      >> >
>      >> > Also we have achieved convergence of -0.000034 with plain GGA and only
>      >> > with MBJ potential we are getting the convergence problem and again
>      >> > plain GGA and also GGA+U have not given the proper electronic structure.
>      >> >
>      >> > As far as the structure is concerned we are very much sure about its
>      >> > structural parameters as they are giving the same XRD as experiment
>      >> > when the positional coordinates and lattice parameters of the 56 atom
>      >> > cell were put into a software powdcell.
>      >> >
>      >> > looking forwards to your comments.
>      >> >
>      >> > with regards,
>      >> > On Mon, Dec 12, 2011 at 12:26 PM, pascal boulet
>      >> > <pascal.boulet at univ-provence.fr <mailto:pascal.boulet at univ-provence.fr>
>      >> > <mailto:pascal.boulet at univ-provence.fr <mailto:pascal.boulet at univ-provence.fr>>> wrote:
>      >> >
>      >> >     Hello,
>      >> >
>      >> >     It is strange that you have such a bad convergence on the energy
>      >> >     and the
>      >> >     charge after that many cycles.
>      >> >     My feeling is that something is wrong in the input.
>      >> >
>      >> >     Have a look at the user manual. From page 205 on, there is an
>      >> >     explanation of the meaning of ghost bands. You have to experiment on
>      >> >     your chemical system to get rid of them.
>      >> >
>      >> >     Pascal
>      >> >
>      >> >
>      >> >     On 12/12/2011 05:21, shamik chakrabarti wrote:
>      >> > > Dear wien2k users,
>      >> > >
>      >> > >                        Any response of my previous mail will be
>      >> > very
>      >> > > helpful for us. Eagerly waiting for your comments.
>      >> > >
>      >> > > with regards,
>      >> > >
>      >> > > ---------- Forwarded message ----------
>      >> > > From: *shamik chakrabarti* <shamikphy at gmail.com <mailto:shamikphy at gmail.com>
>      >> > <mailto:shamikphy at gmail.com <mailto:shamikphy at gmail.com>>
>      >> > > <mailto:shamikphy at gmail.com <mailto:shamikphy at gmail.com> <mailto:shamikphy at gmail.com <mailto:shamikphy at gmail.com>>>>
>      >> > > Date: Sun, Dec 11, 2011 at 5:42 PM
>      >> > > Subject: not getting convergence with MBJ potential
>      >> > > To: A Mailing list for WIEN2k users
>      >> > <wien at zeus.theochem.tuwien.ac.at <mailto:wien at zeus.theochem.tuwien.ac.at>
>      >> > <mailto:wien at zeus.theochem.tuwien.ac.at <mailto:wien at zeus.theochem.tuwien.ac.at>>
>      >> > > <mailto:wien at zeus.theochem.tuwien.ac.at <mailto:wien at zeus.theochem.tuwien.ac.at>
>      >> > <mailto:wien at zeus.theochem.tuwien.ac.at <mailto:wien at zeus.theochem.tuwien.ac.at>>>>
>      >> > >
>      >> > >
>      >> > > Dear wien2k users,
>      >> > >
>      >> > >                        I am trying to simulate electronic
>      >> >     structure of
>      >> > > a charge transfer insulator. Our system consists of a unit cell
>      >> >     having
>      >> > > 56 atoms and we are using 14 k-points. As GGA+U method was failed
>      >> > to
>      >> > > reproduce the proper band gap (in fact much less than the
>      >> > > experimentally obtained one) we have opted for MBJ potential.
>      >> > > *Initially the mixing parameter was set to 0.2 and we got Ghost
>      >> > band
>      >> > > error after few iterations. Hence we reduce the mixing parameter
>      >> > to
>      >> > > 0.15.* Until now still it has shown no error except some extra
>      >> >     message
>      >> > > in case.dayfile. I am giving those messages below. So far e.c. &
>      >> > c.c
>      >> > > were achieved up to 2.239... & 5.4599 respectively and already 36
>      >> > > iterations are over. My questions are:
>      >> > >
>      >> > > (1) Is it ok to set up a mixing parameter of 0.15 that is with
>      >> >     it, is
>      >> > > it possible to reach convergence?
>      >> > >
>      >> > > (2) As plain GGA takes around 80 iterations to converge, is it
>      >> > that
>      >> > > MBJ potential will take much higher than that as we know it is
>      >> >     always
>      >> > > hard to get convergence with this method?
>      >> > >
>      >> > > (3) what are the meanings of the given messages below:
>      >> > >
>      >> > >   lapw2 -c -up   -vresp (17:12:13) >   lapw1  -c -dn    (16:19:33)
>      >> > > 10848.369u 98.026s 52:39.78 346.4%0+0k 0+1099920io 0pf+0w
>      >> > > >   lapw1  -c -up    (15:26:49) 10864.462u 99.082s 52:44.39
>      >> >     346.4%0+0k
>      >> > > 0+1100232io 0pf+0w
>      >> > > 460.324u 151.313s 6:52.62 148.2%0+0k 0+732368io 0pf+0w
>      >> > >  -5.956509016536202E-002
>      >> > >   3.325214690385789E-002 -9.166205529297161E-002 tauwrong=
>      >> > >  int:rho,tauw,grho,g2rho  2.146196813781874E-002
>      >> >      1.287982148952303E-002
>      >> > >  -4.564940741427861E-002
>      >> > >   3.061850458947012E-002 -5.357427363703868E-002 tauwrong=
>      >> > >  int:rho,tauw,grho,g2rho  1.778719641126464E-002
>      >> > >  1.317651193616000E-002        *what is tauwrong?*
>      >> > >  -4.561631481999567E-002
>      >> > >   3.051935798833875E-002 -5.372842413400847E-002 tauwrong=
>      >> > >  int:rho,tauw,grho,g2rho  1.783702549056333E-002
>      >> >      1.305474408433668E-002
>      >> > >  -2.872847342414767E-002
>      >> > >   2.625149916992486E-002 -2.271097056901070E-002 tauwrong=
>      >> > >  int:rho,tauw,grho,g2rho  1.456340274765583E-002
>      >> >      1.183001700580401E-002
>      >> > >  -2.843529510619935E-002
>      >> > >   2.607602777746414E-002 -2.279192386903682E-002 tauwrong=
>      >> > >  int:rho,tauw,grho,g2rho  1.462794826548238E-002
>      >> >      1.162089194449066E-002
>      >> > >  -1.211083415464120E-002
>      >> > > ..........................................
>      >> > > ..........................................
>      >> > > >   lapw0 (15:19:56)  sphere:rho,tauw,grho,g2rho
>      >> > 7.46875999972237
>      >> > >      180.956718336004
>      >> > > >   lapw0 -grr (15:15:10) 315.375u 93.253s 4:45.73 143.0%0+0k
>      >> > > 0+................
>      >> > >
>      >> > >
>      >> > > Any response in this regard will be very helpful for us. Thanks in
>      >> > > advance.
>      >> > >
>      >> > > with regards,
>      >> > > --
>      >> > > Shamik Chakrabarti
>      >> > > Senior Research Fellow
>      >> > > Dept. of Physics & Meteorology
>      >> > > Material Processing & Solid State Ionics Lab
>      >> > > IIT Kharagpur
>      >> > > Kharagpur 721302
>      >> > > INDIA
>      >> > >
>      >> > >
>      >> > >
>      >> > > --
>      >> > > Shamik Chakrabarti
>      >> > > Senior Research Fellow
>      >> > > Dept. of Physics & Meteorology
>      >> > > Material Processing & Solid State Ionics Lab
>      >> > > IIT Kharagpur
>      >> > > Kharagpur 721302
>      >> > > INDIA
>      >> > >
>      >> > >
>      >> > > _______________________________________________
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>      >> > <mailto:Wien at zeus.theochem.tuwien.ac.at <mailto:Wien at zeus.theochem.tuwien.ac.at>>
>      >> > > http://zeus.theochem.tuwien.ac.at/mailman/listinfo/wien
>      >> >
>      >> >     --
>      >> >     Dr. pascal Boulet, computational chemist
>      >> >     University of Aix-Marseille I
>      >> >     Laboratoire Chimie Provence, UMR 6264
>      >> >     Group of Theoretical Chemistry
>      >> >     Avenue Normandie-Niemen
>      >> >     13397 Marseille Cedex 20
>      >> >     France
>      >> >     **********
>      >> >     Tel. (+33) (0)413.55.18.10
>      >> >     Fax. (+33) (0)413.55.18.50
>      >> >     **********
>      >> > http://www.lc-provence.fr
>      >> > https://sites.google.com/a/univ-provence.fr/pb-comput-chem
>      >> >     %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
>      >> >
>      >> >        * Français - détecté
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>      >> >
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>      >> >
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>      >> >     _______________________________________________
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>      >> >
>      >> >
>      >> >
>      >> >
>      >> > --
>      >> > Shamik Chakrabarti
>      >> > Senior Research Fellow
>      >> > Dept. of Physics & Meteorology
>      >> > Material Processing & Solid State Ionics Lab
>      >> > IIT Kharagpur
>      >> > Kharagpur 721302
>      >> > INDIA
>      >> >
>      >> >
>      >> > _______________________________________________
>      >> > Wien mailing list
>      >> > Wien at zeus.theochem.tuwien.ac.at <mailto:Wien at zeus.theochem.tuwien.ac.at>
>      >> > http://zeus.theochem.tuwien.ac.at/mailman/listinfo/wien
>      >>
>      >> --
>      >> Dr. pascal Boulet, computational chemist
>      >> University of Aix-Marseille I
>      >> Laboratoire Chimie Provence, UMR 6264
>      >> Group of Theoretical Chemistry
>      >> Avenue Normandie-Niemen
>      >> 13397 Marseille Cedex 20
>      >> France
>      >> **********
>      >> Tel. (+33) (0)413.55.18.10
>      >> Fax. (+33) (0)413.55.18.50
>      >> **********
>      >> http://www.lc-provence.fr
>      >> https://sites.google.com/a/univ-provence.fr/pb-comput-chem
>      >> %%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
>      >>
>      >> _______________________________________________
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>      >> http://zeus.theochem.tuwien.ac.at/mailman/listinfo/wien
>      >
>      >
>      >
>      >
>      > --
>      > Shamik Chakrabarti
>      > Senior Research Fellow
>      > Dept. of Physics & Meteorology
>      > Material Processing & Solid State Ionics Lab
>      > IIT Kharagpur
>      > Kharagpur 721302
>      > INDIA
>      >
>      > _______________________________________________
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>      > http://zeus.theochem.tuwien.ac.at/mailman/listinfo/wien
>      >
>
>
>
>     --
>     Professor Laurence Marks
>     Department of Materials Science and Engineering
>     Northwestern University
>     www.numis.northwestern.edu <http://www.numis.northwestern.edu> 1-847-491-3996
>     "Research is to see what everybody else has seen, and to think what
>     nobody else has thought"
>     Albert Szent-Gyorgi
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>
>
>
>
> --
> Shamik Chakrabarti
> Senior Research Fellow
> Dept. of Physics & Meteorology
> Material Processing & Solid State Ionics Lab
> IIT Kharagpur
> Kharagpur 721302
> INDIA
>
>
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-- 

                                       P.Blaha
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Peter BLAHA, Inst.f. Materials Chemistry, TU Vienna, A-1060 Vienna
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